CN106700061A - Synthesis method of green modified nonylphenol polyoxyethylene ether - Google Patents
Synthesis method of green modified nonylphenol polyoxyethylene ether Download PDFInfo
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- CN106700061A CN106700061A CN201710045305.8A CN201710045305A CN106700061A CN 106700061 A CN106700061 A CN 106700061A CN 201710045305 A CN201710045305 A CN 201710045305A CN 106700061 A CN106700061 A CN 106700061A
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- modified
- npe
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2230/00—Compositions for preparing biodegradable polymers
Abstract
The invention discloses a synthesis method of green modified nonylphenol polyoxyethylene ether. The method comprises the following steps that (1) a certain proportion of glucose is put into a reaction kettle, dissolved with an appropriate amount of deionized water, and stirred to allow a reaction system to be uniform; (2) an appropriate amount of catalyst is added; moderate temperature is controlled; nonylphenol is dropwise added; the reaction temperature is kept; and curing is performed for 30 min; and (3) heating is performed to reach 100-120 DEG C; dehydration is performed for 1 h; certain temperature and pressure are controlled; ethylene oxide is continuously introduced; the reaction temperature is kept; curing is performed for 1 h; an appropriate amount of acid is added to adjust PH (potential of hydrogen) of a material; and then the material is discharged. By means of the synthesis method, nonyl phenol is modified by introducing the initiator, that is, glucose, so that the problem that the original nonylphenol polyoxyethylene ether product easily decomposes nonyl phenol is solved; a danger coefficient of the product is reduced; the problems of toxicity and environment pollution of the initiator are solved; and high properties of the traditional product are inherited .
Description
First, technical field
The invention belongs to technical field of chemical synthesis, and in particular to a kind of synthesis side of the modified NPE of green
Method.
2nd, background technology
NPE is a kind of nonionic surfactant, with good infiltration, emulsification, dispersion, antiacid, anti-
Alkali, hard water resistance, anti-reduction, oxidation resistance, are widely used in washing, printing and dyeing and chemical field.Existing nonyl phenol gathers
The synthetic method of oxygen vinethene is, with nonyl phenol and oxirane as raw material, to be polymerized under catalyst action.This kind of side
The APEO of method synthesis can decomposite nonyl phenol in natural environment, and nonyl phenol is a kind of generally acknowledged environmental hormone, it
Estrogen can be simulated, biological sexual development is influenceed, there is toxicity to reproductive system.
3rd, the content of the invention
It is an object of the invention to provide the synthetic method of the modified NPE of green, using being modified that the method synthesizes
NPE, be difficult to decomposite nonyl phenol in natural environment, it is to avoid the problems that nonyl phenol is brought.
To achieve the above object, the technical solution adopted by the present invention is：The method comprises the following steps：
1. to a certain proportion of glucose is put into reactor, dissolved using appropriate amount of deionized water, and made by stirring anti-
Answer system homogeneous；
2. proper catalyst is added, control proper temperature is added dropwise nonyl phenol, keeps reaction temperature to continue to cure 30 after completion of dropping
Minute；
3. it is warming up to 100-120 DEG C to be dehydrated 1 hour, control uniform temperature and pressure are continuously passed through oxirane, have led to epoxy second
Keep reaction temperature to cure after alkane 1 hour, discharged after being subsequently adding appropriate amount of acid regulation material PH.
Above-mentioned steps 3. in be passed through the degree of polymerization of oxirane for 2-20, preferred degree of polymerization is 4-10.
Above-mentioned steps 3. before middle discharging the pH value control of material in 5.00-8.00, preferably pH value is 5.50-7.00.
2. middle dropwise addition nonyl phenol and holding reaction temperature are 40-80 DEG C to above-mentioned steps, and preferable temperature is 55-65 DEG C.
Above-mentioned glucose：Nonyl phenol：Deionized water=1: 0.4-0.8:9.5-13.2, aforementioned proportion is mol ratio.
Above-mentioned glucose：Catalyst=1:0.01-0.10, aforementioned proportion is mol ratio.
Above-mentioned steps 3. in the temperature that controls when being passed through oxirane be 90-140 DEG C, preferable temperature is 115-125 DEG C.
Above-mentioned steps 3. be passed through oxirane when the pressure that controls be≤0.50MPa, preferably pressure is≤0.35MPa.
Above-mentioned steps 2. used in catalyst be alkali metal hydroxide, the hydroxide of alkaline-earth metal, alkali metal
Alkoxide, organic alkali catalyst and it is therein two or more；Wherein alkali metal hydroxide is potassium hydroxide, hydrogen-oxygen
Change sodium, lithium hydroxide；The hydroxide of alkaline-earth metal is magnesium hydroxide, calcium hydroxide；The alkoxide of alkali metal be sodium methoxide,
Caustic alcohol, potassium methoxide, glycerine potassium alcoholate；Organic alkali catalyst be monoethanolamine, diethanol amine, triethanolamine, dimethylamine, trimethylamine,
Diethylamine, triethylamine.
Above-mentioned steps 3. used in acid be formic acid, acetic acid, benzoic acid or citric acid.
Synthetic method of the present invention has the following advantages that：
1st, it is modified by introducing initiator glucose n nonylphenol, solves original NPE class product
The problem of nonyl phenol is easily decomposited, the danger coefficient of product is reduced, not only solves that initiator is poisonous, easy pollution environment difficulty
Topic, also inherits the premium properties of traditional product.
2nd, it is modified by introducing initiator glucose n nonylphenol, makes NPE class product in nature
Realize degradable, the environmental-protecting performance of product is greatly improved, and solves the environmental issue of the product traditional handicraft.
4th, specific embodiment
Embodiment 1：
To glucose 180g is put into 2L autoclaves, dissolved using 200g deionized waters, and reaction is made by stirring
System is homogeneous, adds catalyst NaOH 0.4g, controls 55-60 DEG C of dropwise addition 110g nonyl phenol, and reaction is kept after completion of dropping
Temperature continues to cure 30 minutes；100-120 DEG C being warming up to afterwards and starting dehydration, dewatering time is about 1 hour, after dehydration is qualified,
120-125 DEG C of keeping temperature, pressure≤0.35MPa are passed through oxirane 440g, keep reaction temperature ripe after having led to oxirane
Change 1 hour, it is discharging after 5.5-6.5 to be subsequently adding about 0.6g formic acid regulation material PH, and yield is 99.5%, and active ingredient is
99.4%。
Embodiment 2：
To glucose 160g is put into 2L autoclaves, dissolved using 180g deionized waters, and reaction is made by stirring
System is homogeneous, adds catalyst sodium methoxide 0.35g, controls 50-55 DEG C of dropwise addition 108g nonyl phenol, and reaction is kept after completion of dropping
Temperature continues to cure 30 minutes；100-120 DEG C being warming up to afterwards and starting dehydration, dewatering time is about 1 hour, after dehydration is qualified,
115-120 DEG C of keeping temperature, pressure≤0.42MPa are passed through oxirane 460g, keep reaction temperature ripe after having led to oxirane
Change 1 hour, it is discharging after 6.5-7.0 to be subsequently adding about 0.8g acetic acid regulation material PH, and yield is 99.2%, and active ingredient is
99.1%。
Embodiment 3：
To glucose 165g is put into 2L autoclaves, dissolved using 188g deionized waters, and reaction is made by stirring
System is homogeneous, adds catalyst diethylamine 0.82g, controls 60-65 DEG C of dropwise addition 86g nonyl phenol, and reaction temperature is kept after completion of dropping
Degree continues to cure 30 minutes；100-120 DEG C is warming up to afterwards and starts dehydration, dewatering time is about 1 hour, after dehydration is qualified, protect
Hold 125-130 DEG C of temperature, pressure≤0.38MPa and be passed through oxirane 380g, reaction temperature curing 1 is kept after having led to oxirane
Hour, it is discharging after 6.5-7.0 to be subsequently adding about 2.4g benzoic acid regulation material PH, and yield is 99.3%, and active ingredient is
99.2%。
Embodiment 4：
To glucose 154g is put into 2L autoclaves, dissolved using 148g deionized waters, and reaction is made by stirring
System is homogeneous, adds catalyst calcium hydroxide 0.55g, controls 65-70 DEG C of dropwise addition 68g nonyl phenol, and reaction is kept after completion of dropping
Temperature continues to cure 30 minutes；100-120 DEG C being warming up to afterwards and starting dehydration, dewatering time is about 1 hour, after dehydration is qualified,
110-115 DEG C of keeping temperature, pressure≤0.34MPa are passed through oxirane 380g, keep reaction temperature ripe after having led to oxirane
Change 1 hour, it is to discharge after 6.5-7.0 to be subsequently adding about 1.7g citric acids regulation material PH, and product yield is 99.1%, effectively into
It is divided into 99.0%.
Claims (10)
1. a kind of synthetic method of the modified NPE of green, the method comprises the following steps：
1. to a certain proportion of glucose is put into reactor, dissolved using appropriate amount of deionized water, and made by stirring anti-
Answer system homogeneous；
2. proper catalyst is added, control proper temperature is added dropwise nonyl phenol, keeps reaction temperature to continue to cure 30 after completion of dropping
Minute；
3. it is warming up to 100-120 DEG C to be dehydrated 1 hour, control uniform temperature and pressure are continuously passed through oxirane, have led to epoxy second
Keep reaction temperature to cure after alkane 1 hour, discharged after being subsequently adding appropriate amount of acid regulation material PH.
2. the synthetic method of a kind of modified NPE of green according to claim 1, it is characterized in that：It is described
Step 3. in be passed through oxirane the degree of polymerization be 2-20.
3. the synthetic method of a kind of modified NPE of green according to claim 1 and 2, it is characterized in that：
3. the pH value of material is controlled in 5.00-8.00 the step before middle discharging.
4. the synthetic method of a kind of modified NPE of green according to claim 1 and 2, it is characterized in that：
2. middle dropwise addition nonyl phenol and holding reaction temperature are 40-80 DEG C to the step, and preferable temperature is 55-65 DEG C.
5. the synthetic method of a kind of modified NPE of green according to claim 1 and 2, it is characterized in that：
The glucose：Nonyl phenol：Deionized water=1: 0.4-0.8:9.5-13.2, aforementioned proportion is mol ratio.
6. the synthetic method of a kind of modified NPE of green according to claim 1 and 2, it is characterized in that：
The glucose：Catalyst=1:0.01-0.10, aforementioned proportion is mol ratio.
7. the synthetic method of a kind of modified NPE of green according to claim 1 and 2, it is characterized in that：
The step 3. in the temperature that controls when being passed through oxirane be 90-140 DEG C, preferable temperature is 115-125 DEG C.
8. the synthetic method of a kind of modified NPE of green according to claim 1 and 2, it is characterized in that：
The step 3. be passed through oxirane when the pressure that controls be≤0.50MPa, preferably pressure is≤0.35MPa.
9. the synthetic method of a kind of modified NPE of green according to claim 1 and 2, it is characterized in that：
The step 2. used in catalyst be alkali metal hydroxide, the hydroxide of alkaline-earth metal, the alkoxide of alkali metal,
Organic alkali catalyst and it is therein two or more；Wherein alkali metal hydroxide is potassium hydroxide, NaOH, hydrogen-oxygen
Change lithium；The hydroxide of alkaline-earth metal is magnesium hydroxide, calcium hydroxide；The alkoxide of alkali metal is sodium methoxide, caustic alcohol, first
Potassium alcoholate, glycerine potassium alcoholate；Organic alkali catalyst is monoethanolamine, diethanol amine, triethanolamine, dimethylamine, trimethylamine, diethylamine, three
Ethamine.
10. the synthetic method of a kind of modified NPE of green according to claim 1 and 2, it is characterized in that：
The step 3. used in acid be formic acid, acetic acid, benzoic acid or citric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710045305.8A CN106700061A (en) | 2017-01-22 | 2017-01-22 | Synthesis method of green modified nonylphenol polyoxyethylene ether |
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| CN201710045305.8A CN106700061A (en) | 2017-01-22 | 2017-01-22 | Synthesis method of green modified nonylphenol polyoxyethylene ether |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249636A (en) * | 2021-11-26 | 2022-03-29 | 泰兴市凌飞化学科技有限公司 | Preparation method of dinonylphenol polyoxyethylene ether as component of heavy-duty oil stain cleaning agent |
Citations (7)
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|---|---|---|---|---|
| US4011389A (en) * | 1975-03-21 | 1977-03-08 | Basf Wyandotte Corporation | Glycoside polyethers |
| CN1313785A (en) * | 1998-06-23 | 2001-09-19 | 联合碳化化学品及塑料技术公司 | Liquid thickener for surfactant systems |
| CN101062469A (en) * | 2006-04-29 | 2007-10-31 | 杭州天成化工有限公司 | Preparation method of methylglucoside polyether series product |
| CN101601984A (en) * | 2009-07-07 | 2009-12-16 | 河北工业大学 | Connect the NPE dimeric surfactant of group with piperazine |
| CN103228667A (en) * | 2010-11-25 | 2013-07-31 | 化工产品开发公司Seppic | Novel hydrotropic agent, use thereof to make non-ionic surfactants soluble, and compositions containing same |
| CN106083948A (en) * | 2016-06-16 | 2016-11-09 | 常熟耐素生物材料科技有限公司 | Two phenol polyethenoxy ether base glucosides and its preparation method and application between pentadecane (alkene) base |
| CN106083947A (en) * | 2016-06-16 | 2016-11-09 | 常熟耐素生物材料科技有限公司 | Phenol polyethenoxy ether glucoside and its preparation method and application between pentadecane (alkene) base |
-
2017
- 2017-01-22 CN CN201710045305.8A patent/CN106700061A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4011389A (en) * | 1975-03-21 | 1977-03-08 | Basf Wyandotte Corporation | Glycoside polyethers |
| CN1313785A (en) * | 1998-06-23 | 2001-09-19 | 联合碳化化学品及塑料技术公司 | Liquid thickener for surfactant systems |
| CN101062469A (en) * | 2006-04-29 | 2007-10-31 | 杭州天成化工有限公司 | Preparation method of methylglucoside polyether series product |
| CN101601984A (en) * | 2009-07-07 | 2009-12-16 | 河北工业大学 | Connect the NPE dimeric surfactant of group with piperazine |
| CN103228667A (en) * | 2010-11-25 | 2013-07-31 | 化工产品开发公司Seppic | Novel hydrotropic agent, use thereof to make non-ionic surfactants soluble, and compositions containing same |
| CN106083948A (en) * | 2016-06-16 | 2016-11-09 | 常熟耐素生物材料科技有限公司 | Two phenol polyethenoxy ether base glucosides and its preparation method and application between pentadecane (alkene) base |
| CN106083947A (en) * | 2016-06-16 | 2016-11-09 | 常熟耐素生物材料科技有限公司 | Phenol polyethenoxy ether glucoside and its preparation method and application between pentadecane (alkene) base |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114249636A (en) * | 2021-11-26 | 2022-03-29 | 泰兴市凌飞化学科技有限公司 | Preparation method of dinonylphenol polyoxyethylene ether as component of heavy-duty oil stain cleaning agent |
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Application publication date: 20170524 |